Cosmetic preparation of active substances with high protection factor against free radicals

ABSTRACT

The disclosed cosmetic preparation of active substances protects the skin in a particularly effective way against free radical aggression, both alone and in combination with other active substances. The preparation consists of a Quebraco blanco bark extract containing at least 90 wt. % proanthocyanidin oligomers, a silkworm extract containing the peptide cecropin, amino acids and a vitamin mixture, a non-ionic, cationic or anionic hydrogel, phospholipids and water, and may also contain further active substances such as vitamin derivatives and plant extracts of acerola, sea weed, citrus, bitter orange, cherry, papaya, tea, coffee beans, Mimosa tenuiflora and angelica. The preparations have protection factors against free radicals of up to 10000, and the cosmetic compositions containing these preparations have protection factors of between 40 and 200, depending on their proportion of the preparations.

The disclosed cosmetic preparation of active substances protects theskin in a particularly effective way against free radical aggression,both alone and in combination with other active substances.

Free radicals such as superoxide ions, hydroxy radicals, oxides areknown as a major factor of degeneration and thus the ageing of the skin.They destruct the proteins and lipids of the cellular membrane, affectthe DNA and also decompose the hyaluronic acid, a key substance of theskin. Under normal biological conditions there is an equilibrium ratiobetween the free radicals coming up and their embankment by endogenouschemical or enzymatic systems. Additional outside stress factors such asaggressive atmosphere, tobacco smoke, ultraviolet radiation etc. mayoverload these inherent immune systems and shift the equilibrium infavour of the free radicals. Inflammation or ageing phenomena of theskin may occur, indicating a need for compensation by cosmetic products.

There has already been proposed a series of products for this purpose,most of them containing mixtures of the vitamins A, C and E or additivesof superoxide dismutase or extracts of certain plants or animals. Thus acosmetic compound containing ultrasound decomposition products of yeastand other cellular dispersions is known from U.S. Pat. No. 5,629,185.From WO96/29048 a cosmetic containing condensed decomposition productsof plants or animals is known. There is also a number of publicationsdescribing the use of pure plant extracts for cosmetic purposes, such asWO97/45100, where a mixture of seven different extracts is described foranti-cellulite treatment.

The search for other effective substances is a major element of cosmeticresearch. Another problem of many of these products is that thesubstances which are effective against free radicals often do not keeptheir catching properties within the ready cosmetic compound, i.e. itrequires special formulations to permanently maintain the effectivenessof the radical catchers.

On the other hand it seems that it has not become widely known in thecosmetic industry yet that there is a possibility of measuring theantioxidant potential of the skin (DE 4328639) and recently also ofdetermining the radical protection coefficient of a cosmetic preparationby using a relatively simple method and to purposefully add materials tosuch a preparation.

It is an object of the present invention to provide a cosmeticpreparation of active substances which has a particularly high radicalprotection potential.

Another objective of the invention is to provide a preparation of activesubstances that keeps its radical protection potential over a longperiod of time.

Another objective of the invention is to provide special cosmeticcompounds containing this preparation of active substances andespecially such preparations of active substances which achieve furtherimprovement of properties, in particular with regard to opening thepores of the skin.

According to the invention, the cosmetic preparation of activesubstances with a high radical protection factor is characterised bycomprising

(a) a product obtained by extraction of the bark of Quebracho blanco andsubsequent enzymatic hydrolysis, containing at least 90 percent byweight of proanthocyanidine oligomers and up to 10 percent by weight ofgallic acid, wherein the content of (a), which is available in aconcentration of 2 percent by weight linked to a microcapsules, rangesfrom 0.1 to 10 percent by weight;

(b) an extract of the silkworm obtained by extraction, containing thepeptide Cecropine, amino acids and a vitamin mix, wherein the content of(b) may range from 0.1 to 10 percent by weight;

(c) a non-ionic, cationic or anionic hydrogel or mixture of hydrogels,wherein the content of (c) may range from 0.1 to 5 percent by weight;

(d) one or several phospholipids comprising 0.1 up to 30 percent byweight;

(e) up to 100 percent by weight of water related to the total weight ofthe active substance preparation each.

As applicable, the active substance preparation may also contain:

(f) an ultrasound decomposition product of a yeast containing 15 atleast 150 units of superoxide dismutase per ml, wherein the content ofthe decomposition product (f) is in the range from 0 to 4 percent byweight;

(g) an extract of acerola fruits Malpighia punidifolia, wherein thecontent (g) is in the range from 0 to 20 percent by weight; and

(h) a mixture of 0.1 percent by weight of liposomal Micrococcus luteusextract, retinyle palmitate and tocopherylacetate prepared withphospholipids and free retinyle palmitate related to the total weight ofthe active substance preparation each.

For one embodiment of the invention comprising the active substancecomponent (h) the portions of the preparation related to the totalweight of the cosmetic are as follows: capsules of the active substanceaccording to (a) ranging from 0.1 to 10 percent by weight, hydrogelaccording to (b) ranging from 0.1 to 5 percent by weight, encapsulatedretinyle palmitate according to (h) 0.001 to 5 percent by weight,encapsulated tocopherylacetate according to (h): 0.001 to 2 percent byweight free retinyle palmitate according to (h): 0.1 to 5 percent byweight, phospholipids: 0.2 to 5 percent by weight, water as theremaining portion up to 100 percent by weight and/or other auxiliary orcarrier substances.

The Quebracho bark extract according to the invention or its hydrolysisproduct has a very high portion of proantho-cyanidines representingcondensed tannins. These compounds appearing as oligomers and the lowportion of gallic acid in this combination and in a concentrationbetween 1 and 10 percent by weight shows a clear radical protectioneffect, which by far exceeds the effect of superoxide dismutase (SOD).The activity against free radicals was compared with that of SOD andfound to be 42% for a 1 percent by weight solution of the extract (SOD4%), 83% for a 2.5% by weight solution (SOD 15%)and 100% for a 5% byweight solution (SOD 38%). Preferably the extract (a) contains at least95 percent by weight of proanthocyanidine oligomers and up to 5 percentby weight of gallic acid, in particular at least 99 percent by weight ofproanthocyanidine oligomers and up to 1 percent by weight of gallicacid.

The content of (a) is 1 to 10 percent by weight, wherein the activesubstance from the Quebracho bark is enclosed in microcapsules. Themicrocapsules may consist of petrolatum, sodium tristearat, agar,phenonip and water.

The silkworm extract (b) is obtained by extraction of the silkworm(Bombvx mori) with 1,2-propylene glycol and contains vitamins, aminoacids and the Cecropine peptide, which has a special antibacterialfunctionality. A range of studies of the haemolymph and the cuticularmatrix of the silkworm carried out during the last years showed that itdoes not only contain antibacterial peptides but also inhibitors, inparticular fungal protease inhibitors. Such extracts also show oxygenconsuming properties, thus activating the cellular metabolism, and theyhave moisture-keeping properties, a clear curative effect on lesions inthe skin by reducing healing time and a skin-smoothing effect.

Preferably, the extract (b) includes the amino acids aspertinic acid,asparagine, threonine, serine, glutaminic acid, praline, glycine,alanine, valine, cysteine, methionine, isoleucine, leucine, tyrosine,phenylalanine, lysine, histidine, arginine.

Preferably extract (b) also contains a vitamin mixture includingvitamins B₁, B₂, B₅, B₆, B₈, B₉, B₁₂, PP, A, E and C.

The concentration of components (a) and (b) in the active substancepreparation preferably ranges from 0.1 to 3 percent by weight each, inparticular from 0.5 to 3 percent by weight. The gel contained accordingto the invention, which may also be a mixture of different gels, is ahydrogel soluble in water at temperatures above 40 up to 50° C.,approximately, and which takes the gel structure at low temperaturesbetween 10 and 30° C. Examples of such gels are non-ionic polymers suchas polyvinyl alcohol, polyvinyl pyrrolidone-modified maize starch andhydroxyethylcellulose, cationic polymers such as cationic Guar, cationiccellulose, synthetic cationic polymers or gels such as gelatine,carrageenan, bentonite gels, copolymeric gels such as carbomer.

The phospholipids contained according to the invention have beenselected among phosphatidyl choline, phosphatidyl ethanolamine,phosphatidyl inositol, phosphatidyl serine, phosphatidic acid andlysolecithines as well as mixtures thereof. Known products arePhoslipone, for example. The contents of phospholipids ranges from 0.1to 30 percent by weight, preferably 0.5 to 20 percent by weight.

The components (a) and (b) of the active substance preparation and thephospholipids (d) presumably form association-like configurations ofdifferent molecules which again are accumulated mostly homogeneously inthe generating structure of the gel (c)+(e), the whole being called“association complex”. This may also include portions of theSOD-containing yeast decomposition product and of the acerola extract aswell as certain plant extracts.

The encapsulated mixture of 0.1 percent by weight of Micrococcus luteusextract, retinyle palmitate and tocopherylacetate is present as liposomeprepared with phospholipids, wherein the content of retinyle palmitateand tocopherylacetate may preferably range from 0.001 to 1 percent byweight. The portion of phospholipids in this encapsulated mixturegenerally ranges between 5 and 40 percent by weight.

Additionally, the preparation of the active substance as an associationcomplex may contain a mixture of the vitamins A, B and C as well asadditional SOD and/or extracts of acerola fruits. However, the completepreparation of the cosmetic preparation may also contain vitamins andother antioxidants.

According to the invention, the active substance preparation may alsocontain, in addition to the basic components (a) through (e), differentplant extracts such as citrus peel or leaf extracts (Citrus bigaradia,Citrus hystrix, Citrus aurantifolia, Citrofurtunella microcarpa, Citrusaurantium, Citrus reticulata), petitgrain extract (peel or fruit),extract of the Spanish cherry, kiwi extract (Actinidia chinensis),papaya fruit- extract (Caricae papayae), tea extract [leaves of green orblack tea, leaves or bark of new jersey tea (Ceanthus velutinas)],coffee bean extract (INCI name: coffee bean extract; of green or roastedbeans), prunus extract (Prunus armeniaca, Prunus dulcis, Prunus persica,Prunus domestica, Prunus spinosa, Prunus serotina, Prunus virginiana),extracts of the bark of the Mexican skin tree (Mimosa tenuiflora),angelica root extract (Angelica archangelica). Such plant extracts arecommercially available, e.g. from DRAGOCO, Holzminden; Germany.

The content of these plant extracts may range from 0 to 40 percent byweight, preferably from 0.1 to 40 percent by weight, in particular 0.5to 20 percent by weight, where the mixture may also contain mixtures ofthese extracts as well as mixtures with the components (f) and (g) ofthe active substance preparation.

Depending on the plant and the added quantity, the addition of the aboveplant extracts may increase the radical protection factor several times,presumably with the occurrence of synergistic interactions, thecorrelation between which we have not been able to find out yetcompletely.

The antioxidants that may be used in the invention include vitamins suchas vitamin C and derivatives of it, such as ascorbylacetates, phosphatesand palmitates; vitamin A and its derivates; folic acid and itsderivates, vitamin E and its derivates, such as tocopherylacetate;flavones or flavonoides; amino acids such as histidine, glycine,tyrosine, tryptophan and derivates of it; carotinoids and carotenes,such as 13-carotin, ct-carotin; uric acid and derivates; a-hydroxy acidssuch as citric acid, lactic acid, malic acid; stilbenes and theirderivates etc.

Vitamins may also be contained in a mixture with enzymes as anotherportion in the active substance preparation or in the cosmeticcomposition apart from the active substance preparation. The content maybe at least be 0.5 percent by weight of a mixture of enzymes andvitamins containing at least 150 units/ml (U/ml) of superoxide dismutase(SOD).

Preferably, the used mixture of enzymes and vitamins is an ultrasounddecomposition product of a yeast, where the decomposition productcontains SOD, protease, vitamin B₂, vitamin B₆, vitamin B₁₂, vitamin D₂and vitamin E. Preferably, it contains at least 150 U/ml of SOD,protease and the vitamins B and D, where the proportion between SOD andprotease as international units at least ranges from 3:1 to 8:1.

Of special advantage for making the enzyme/vitamin mixture is anultrasound-based decomposition method described in DE 4241154C1, where acellular dispersion or suspension is passed through a continuousultrasound irradiation cell, where the sonotrode protects up to half ortwo thirds of its length into the cell and is submerged in the medium tobe exposed to ultrasound-irradiation. The sonotrode has an angle of 80.5to 88.5 degrees, and the correlation between the submerged length in mmof the sonotrode and the exposed volume in ml is set to a value rangingfrom 1:1.1 o 1:20. The portion of solid particles in the medium to beexposed to acoustic irradiation ranges from 1:0.02 to 1:2.2 percent byweight.

Yeasts such as baker's yeast, brewing yeast, wine yeast as well asspecially treated yeasts such as SOD-enriched yeasts can be used ascellular dispersions. For instance, a cellular dispersion that can bepreferably used may contain Saccharomyces cerevisiae.

The addition, for instance, of 1 percent by weight of such a yeastdecomposition product of baker's yeast as an optional portion of theassociation complex may nearly double a radical protection factor, whichitself is high already, from 1620 to 3150. Further remarks on theradical protection factor will be made below. In addition to the abovecomponents the active substance preparation in the form of theassociation complex may also contain an extract of acerola fruits(Malpighia punidifolia). Acerola is a small tree indigenous to the WestIndies, to northern South America, to Central America, Florida andTexas, which is rich in vitamin C and other active substances such asVitamin A, thiamine, riboflavine and niacine, which may develop acomplex activity together with different other components such asphosphor, iron, calcium. The aqueous acerola extract is normallyavailable as a powdered product. As another active substance in thecomplete composition of the cosmetic preparation and in addition to theabove active substance complex an especially preferred embodiment maycontain one or several of the following components:

(1) extracts or treated extracts of plants binding free radicals ormoisture, selected among acerola fruits (Malpighia punidifolia),Camellia oleifera, Colunsonia canadensis and Hibiscus sabdariffa;

(2) extracts or treated extracts of algae binding free radicals ormoisture, selected among omega plankton with a high content ofcerebrosid stimulants, micro algae of the chlorella species and macroalgae of the ulva species associated with byssus (mussel silk) asbiotechnological protein fraction and subsequently associated withdextrine, wherein the product appears in the mixture with peptidederivates derived from a-MSH and associated with xanthin.

(3) natural and synthetic polymers selected among chitosanglycolate,condensed products of desiccated milk, and activated fatty acids,

(4) magnetically hard single crystals of bariumhexaferrite having acoercitive field strength of 3000-5000 Oe and a grain size of 50-1200 nmintercalated in or mixed with asymmetric lamellar aggregates forphospholipids and fluorocarbons as well as

(5) other active substances and carriers selected among hyaluronic acid,omega CH activator, behentrimonium chloride, passion flower oil as wellas modified kaolin.

The mentioned modified kaolin is contained according to W096/17588 andhas been modified with spherical TiO₂or SiO₂ particles having a size of<5 μm, wherein the spherical particles's share in the kaolin mixtureranges from 0.5 to 10 percent by weight. This is what makes thepreparation feel very smooth on the skin and gives it additionalanti-inflammatory functionality. The modified kaoline may amount to acontent ranging from 0.1 to 6 percent by weight of the total quantity ofthe cosmetic.

The mentioned magnetically hard particles for stimulating thecirculation of the blood may be such as described in W095/03061 or suchwith smaller particle sizes and in a mixture with asymmetric lamellaraggregates charged with oxygen up to the saturation pressure, where thecontent of magnetic particles related to the total composition of thecosmetic may range from 0.01 to 10 percent by weight.

The mentioned asymmetric lamellar aggregates are known from W094/00098and consist of phospholipids and fluorocarbon charged with oxygen or afluorocarbon mixture. The fluorocarbon content is in the range from 0.2to 100 percent by weight/volume, wherein the phospholipid has aphosphatidyl choline content of more than 30 up to 99 percent by weightand where these aggregates have a skin penetration depending on thecritical solubility temperature of the fluorocarbons.

In addition, the aggregates may also appear alone in the cosmeticpreparation only charged with oxygen. The content may range from 2.5 to20 percent by weight of the total composition of the cosmetic.

These aggregates are oxygen carriers and allow the penetration of theoxygen into the skin, thus improving oxygen supply to the skin.

The preparation according to the invention further contains cosmeticauxiliary substances and carriers as normally used in such preparations,e.g. water, glycerine, propylene glycol, preserving agents, colorants,pigments with colouring effect, thickeners, softening substances,moisture-preserving substances, aromatic substances, alcohols,polyalcohols, electrolytes, polar and non-polar oils, polymers,copolymers, emulsifiers, waxes, stabilisers, tinted plant extracts suchas fat-soluble gardenia extract, fat-soluble carrot extract, paprika LSextract, B-carotene, lithospermum extract and active deodorants.

It is also advantageous to add suitable water-soluble and/or oil-solubleUVA or IVB filters or both to the composition according to theinvention. Among advantageous oil-soluble UVB filters are 4-aminobenzoicacid derivates such as the 4-(dimethylamino) benzoic acid (2-ethylhexyl)ester, ester of the cinnamic acid such as the 4-methoxycinnamic acid(2-ethyl-hexyl)ester, benzophenone derivates such as2-hydroxy-4-methoxybenzophenone, 3-benzylidene camphor derivates such as3-benzylidene camphor.

Water-soluble UVB filters are for instance sulfonic acid derivates ofbenzophenone or of 3-benzylidene camphor or salts such as the Na or Ksalt of the 2-phenylbenzimidazol-5-sulfonic acid.

UVA filters include dibenzoylmethane derivates such as1-phenyl-4-(4′-isopropylphenyl )propane-1,3-dione.

Preferred solar radiation protection filters are inorganic pigments onthe basis of metal oxides such as TiO₂, SiO₂, ZnO, Fe₂O₃, ZrO₂, MnO,Al₂O₃, which can also be used as a mixture with each other or withorganic filters. Particularly preferred inorganic pigments areagglomerated substrates of TiO₂and/or ZnO, having a contents ofspherical and porous SiO₂ particles, wherein the SiO₂ particle sizeranges from 0.05 μm to 1.5 μm and where apart from the SiO2 particlesthere are inorganic particle-type substances of a spherical structure,where the spherical SiO₂ particles form defined agglomerates with otherinorganic substances having a particle size ranging from 0.06 μm to 5μm.

Particularly advantageously used SiO₂ particles are highly monodisperse,non-porous, spherical SiO₂ particles according to DE 3616133, producedby hydrolytic polycondensation of tetraalkoxy silane in an aqueousalcoholic-ammoniacal medium, where a sol of primary particles isgenerated, which subsequently brings the contained SiO₂ particles to thedesired particle size of about 0.05 up to 10 μm by continuously addingtetraalkoxy silane proportioned in a controlled way, depending on thereaction.

Pigments, pigment mixtures or powders with pigment-like functionality,also comprising those having a pearlescent effect, may also comprisesubstances such as: mica, kaolin, talcum powder, mica-titanium oxide,mica-titanium oxide-iron oxide, bismuth oxychloride, nylon globules,ceramic globules, expanded and non-expanded synthetic polymer powders,powdery natural organic compounds such as pulverized hard algae,encapsulated and non-encapsulated cereal starches and mica-titaniumoxide-organic dye.

Normally, a wide range of compounds may be used as softeners, such asstearyl alcohol, glyceryl monoricinoleate, glyceryl monostearate,1,2-propanediol, 1,3-butandiol, cetylic alcohol, isopropyl isostearate,stearic acid, isobutyl palmitate, oleyl alcohol, isopropyl laurate,decyloleate, 2-octadecanol, isocetylic alcohol, cetylic palmitate,silicon oils such as dimethylpolysiloxane, isopropyl myristate,isopropyl palmitate, polyethylene glycol, lanoline, cacao butter,vegetable oils such as maize oil, cotton seed oil, olive oil, mineraloils, butyl myristate, palmitic acid etc.

Cosmetic preparations with the preparation of the active substanceaccording to the invention may exist as O/W or W/O emulsions. Suitableemulsifiers for O/W emulsions are for instance addition products of 2-30mol ethylene oxide to linear C₈-C₂₂ fatty alcohols, to C₁₂-C₂₂ fattyacids and to C₈-C₁₅ alkylphenols; C₁₂-C₂₂ fatty acid monoesters anddiesters of addition products of 1-30 mol ethylene oxide to glycerineGlycerine monoesters and diesters as well as sorbitan monoester anddiester of C₆-C₂₂ fatty acids, polyol- and polyglycerinester; additionproducts of ethylene oxide to castor oil; betaines such as coconut alkyldimethyl ammonium glycinate or coconutacylaminoethylhydroxyethylcarboxymethyl-glycinate (CTFA: cocamidopropylbetaines) as well as ampholytic tensides.

Suitable emulsifiers for W/O emulsions are for instance additionproducts of 2-15 mol ethylene oxide to castor oil, esters of C₁₂-C₂₂fatty acids and glycerine, polyglycerin, pentaerythrite, sugar alcohols(e.g. sorbite), polyglucosides (e.g. cellulose), polyalkylene glycols,wool alcohols, copolymers of polysiloxan polyalkyl polyether.

The water content of a preparation with the active substance complex mayvary within a wide range and is preferably between 5 and 90 percent byweight, where a lower water content of about 0.5-8 percent by weight maybe found in particular in lipsticks.

The especially preferable cosmetic preparation with the active substancecomponent (f) is a particularly effective protection against the attackof free radicals on the skin both alone and in combination with otheractive substances and has a surprising effect on the opening of thepores of the skin, similar to the effect of a cleaning means (peeling).This increases the efficiency of other properties by further ingredientsof the cosmetic preparation, like improved moisturizing and smoothing ofthe skin, thus improving even more and for a longer time the entirestate of the skin.

It was also surprising that the retinyle palmitate in both encapsulatedand in non-encapsulated form is effective in the upper and lower layersof the skin at the same time and maintains this effectiveness over alonger period of time, thus improving the repair effect of theassociation complex. The latter seems to be due to the presence oftocopherylacetate, since only in this combination the simultaneous andlasting effect could be observed.

The preparation of the active cosmetic substance according to theinvention, when applied either alone or in combination with other activesubstances, protects the skin in a particularly efficient way againstthe attack of free radicals on the skin. It has a high radicalprotection factor between 100 and 3500×10¹⁴ Radicals/mg.

The radical protection factor (RPF) determines the activity of asubstance for binding free radicals as compared with a test substance.The test substance consists of a highly reactive, semi-stable radical,which reacts with all known antioxidants. Such radicals includenitroxides such as proxo(2,2,5,5-tetramethyle-l-dihydropyrrolinoxy-nitroxide), tempol(2,2,6,6-tetramethyl-1-piperidinoxy-4-ol-nitroxide), DTBN(ditert-butyl-nitroxide) or preferably DPPH(1,1-diphenyl-2-picryl-hydrazyl).

The RPF is determined by measuring the signal amplitude of the testradical by electron spin resonance (ESR/EPR) before and after mixingwith an antioxidant and by calculating the RPF on this basis. For aseries of standard antioxidants the RPF is a known parameter, so it is827 for all-trans-retinole, 196 for all-trans retinal acetate, 41200 forDL-α-tocopherol and about 48 for a-tocopherol acetate, each ×10¹⁴radicals/mg.

The preparation of the active cosmetic substance alone, if existing as“association complex” of the components (a) through (e) and in aconcentration of 10 percent by weight of (a) and (b) each has an RPF of1255, which is very high as compared with common active substances incosmetic formulations with declared radical scavengers, which achievevalues of about 4 to 40. This is the case even though the concentrationof the active substances themselves in (a) and (b) is only 2 percent byweight, as a maximum. “High radical protection factor” according to thepresent invention means a value of 100 or higher, preferably 1000 orhigher. In certain combinations of plant extracts and the associationcomplex itself according to the present invention this value may beincreased to 10000 and higher. Depending on the portion of thepreparation, the corresponding cosmetic compositions with suchpreparations comprise radical protection factors, for example, from 40to 200 or higher. The exact method for measuring the radical protectionfactor has been described by Herrling, Groth, Fuchs and Zastrow inConference Materials “Modern Challenges To The Cosmetic Formulation”5.5.-7-5.97, Düsseldorf, p. 150-155, Verlag f. chem. Ind. 1997. Startingfrom the known concentration of the test substance (here: DPPH) or thenumber of its free radicals (radicals per ml) they measure a signalamplitude S₁ with an ESR spectrometer. The test radical and theantioxidant are dissolved in a water/alcohol solution (e.g. 0.1 m) each.The signal amplitude S₂ of the antioxidant is measured. The normaliseddifference between the two signal amplitudes is the reduction factor RF.

RF=(S ₁ −S ₂)/S₁

The result of the radical reduction of the test substance RC ×RF isnormalised relative to the quantity of product input PI (mg/ml). WhereRC is the amount of the test substance, i.e. the known number ofradicals in the test substance. The radical protection factor iscalculated by means of the following equation:${RPF} = \frac{{{RC}\quad\left\lbrack {{Radicals}/{ml}} \right\rbrack} \times {RF}}{{PI}\quad\left\lbrack {{mg}/{ml}} \right\rbrack}$

The result is

RPF=N×10¹⁴[Radicals per mg],

where N is a positive real number and RPF for simplification may bereduced to the value of N. This reduction has been used in the examplesof the present invention.

The radical protection factor may be determined by means of a handy andvery simple ESR spectrometer (GALENUS GmbH, Berlin, Germany) and is anew magnitude for characterising cosmetic products as regards theircapacity of binding free radicals. The method is an in vitro method,where no individual properties of the user of the cosmetic areinfluencing the antioxidants.

Other advantageous effects of products with the active substancepreparation according to the invention, in combination with other activesubstances or carriers are a lasting improvement of the general state ofthe skin, a delayed ageing process of the skin, lasting improvement ofthe moisturizing and smoothing effect on the skin. The particularlyadvantageous embodiment described above with an additional algae-peptideproduct and magnetically hard single crystals of bariumhexaferritecomprises a special allergy-reduced risk, according to allergy anddermatological tests.

The cosmetic preparation according to the invention may be used, forexample, in sun creams, sun gels, after-sun products, day creams, nightcreams, masks, body lotions, cleansing milk, makeup's, lipsticks, eyecosmetics, hair masks, hair conditioners, shampoos, shower gels, showeroils, bathing oils and other common products. A particular advantage ofthe active substance preparation according to the invention is theembodiment with the optional component (f) in a cream, lotion, a makeup,fluid, gel or lipstick. Advantageous cosmetic preparations also includetooth pastes mouthwash, under the special aspect of neutralising freeradicals in the mouth of smokers and also as special cream for the handsand the face of smokers. Such products are manufactured in a way knownby workers skilled in the art. When selecting special carriersubstances, the corresponding pharmaceutical preparations may also bemade.

Another subject matter of the invention is a cosmetic preparationcomprising a content of plant extract selected from the group comprisingcitrus extract, petitgrain extract, cherry extract of the Spanishcherry, papaya fruit extract, tea extract, coffee bean extract, prunusextract, skin tree extract, angelica extract and mixtures of them as hasbeen defined more in detail above, with a content of 0.5 to 40 percentby weight as well as 99.5 to 60 percent by weight of other activesubstances or carriers or mixtures of active substances and carriersubstances, each related to the total composition. Active and carriersubstances may be the substances mentioned above.

The following examples are to illustrate the invention more in detail.If not otherwise indicated, all measures will be given in percent byweight.

Manufacture of the Active Substance Complex

For making the gel basis, gel powder such as carbomer was added towater, homogenised and subsequently neutralised with triethanolamine,for example. Then ethanol and glycerine were added to improve mixingproperties, and the mixture was well stirred.

To this gel basis a mixture of phospholipids (Phoslipone), Quebrachoextract and silkworm extract was added and mixed at a temperature of upto 45° C. Then another portion of the above gel or a second gel such asGuar propyl triammonium chloride was added and stirred well with thewhole mixture at increased temperature, but below 45° C. This way yougot the active substance preparation according to the invention,hereinafter called “complex”.

In those cases where the active substance preparation contained otheringredients such as yeast decomposition product, acerola extract orextracts of tea, coffee, kiwi, citrus, cherry, papaya or skin tree, suchextract was added to the mixture of phospholipids and mixed with thegel.

EXAMPLE 1

Day cream

phase A: carbomer 0.2; glycerine 2.0; propylene glycol 1,0; dist. waterq.s. ad 100;

phase B: C₁₂-C₁₅-alkyl cetylic alcohol 3,7; stearate 0,5; jojoba oil1,0;

phase C: triethanolamine 0,2;

phase D: active substance complex with (a) through (f) 3.5perfume 0.5;preservant 0.3

Phases A and B were warmed up to 65±2° C. while being stirred, and phaseB was homogenised in phase A. Then phase C was added and homogenisedcorrespondingly. Subsequently, the mixture was cooled down to 35° C.while being stirred, and phase D was added and mixed thoroughly. Theactive substance complex contained 1.0% of an SOD-containingenzyme/vitamin product obtained from baker's yeast using the ultrasoundmethod according to DE 4241154C1.

The added active substance complex contained 1% of dry gel, 7% ofphospholipids, 2% of Quebracho extract, 1% of silkworm extract, 1% ofSOD from a yeast decomposition product. The radical protection factor ofthis active substance complex amounted to 1925, and in the formulationthe RPF was around 49.

EXAMPLE 2

Special Cream

phase A: glycerine 3.0; dist. water q.s. ad 100;

phase B: Vaseline 22.5; jojoba oil 5.0;

phase C: active substance complex with (a) through (f) 5.5; asymmetriclamellar aggregates (AOCS) according to example 2 of W094/00109 10.5;AOCS with Ba hexaferrite single crystals according to example 1 ofW095/03061, 2.0; modified kaolin according to example 1 of W096/175880,3.

Phases A and B were warmed up to 65±2° C. while being stirred, and phaseB was homogenised in phase A. Subsequently, the mixture was cooled downto 35° C. while being stirred, and phase C was added and mixedthoroughly.

The active substance complex contained 1.0 % of an SOD-containingenzyme/vitamin product obtained from wine yeast using the ultrasoundmethod according to DE 4241154C1 and in addition 0.5% of vitamin E and0.5% of vitamin C. The basic ingredients of the active substance complexwere 0.5% of dry gel, 10% of phospholipids, 1% of Quebracho extract, 2%of silkworm extract. The radical protection factor of this activesubstance complex amounted to 2120, and in the formulation the RPF wasaround 41.5.

EXAMPLE 3

Sun Gel

phase A: carbomer 1.5; glycerine 3.0; propylene glycol 2.5; dist. waterq.s. ad 100;

phase B: triethanolamine 1,5;

phase C: peptide preparation MAP-XE according to PCT/DE97/02941 1,0; ZnO2.0; TiO₂ 5.0; SiO₂ 1.0; shellac (20% aqueous solution) 1.0;

phase D: active substance complex with (a) through (f) 3,5;

phase E: perfume 0.5, preservant 0,3.

Phase A was warmed up to 60±2° C. while being stirred and homogenisedand cooled down to 45° C. Phase B was homogenised in phase A. Aftercooling down to about 40° C., phase C was added and the mixture was wellhomogenised. Subsequently, the mixture was cooled down to 35° C. whilebeing stirred, and phases D and E were added and mixed and stirredthoroughly. The active substance complex contained 1.0 % of anSOD-containing enzyme/vitamin product obtained from brewer's yeast usingthe ultrasound method according to DE 4241154C1 and in addition 0.5 % ofvitamins E, vitamin C and vitamin A, each. The basic ingredients of theactive substance complex were 0.15% of dry gel, 20% of phospholipids, 5%of Quebracho extract, 3% of silkworm extract. The radical protectionfactor of this active substance complex amounted to 3050.

EXAMPLE 4

Day Cream

A composition according to example 1 was made, with the active substancecomplex containing 20% of black tea extract instead of 1% of SOD of ayeast decomposition. The radical protection factor of this activesubstance complex amounted to 3100.

EXAMPLE 5

Sun Cream

A composition according to example 1 was made, wherein phase A containedan additional 3% of TiO₂ and 7.5% of benzophenone-3. Instead of 1% ofSOD of a yeast decomposition, the active substance complex contained 5%of coffee bean extract of roasted coffee beans and 2% of kiwi extract.The radical protection factor of this active substance complex amountedto 3200.

EXAMPLE 6

Day Cream

A composition according to example 1 was made, wherein phase A containedan additional 1% of TiO₂ and 0.5% of ZnO. Instead of 1% of SOD of ayeast decomposition, the active substance complex contained 1% of greentea extract, 2% of an extract of green coffee beans, 1% of vitamin C and1% of vitamin E (tocopherolacetate). The radical protection factor ofthis active substance complex amounted to 5600.

EXAMPLE 7

Example for Comparison Purposes

The following components of an active substance complex were mixed witheach other:

0.15% of guar propyl triammonium chloride (gel); 20% of phospholipids;0.1% of triethanolamine; 1.0% of vitamin E; 0.1% of vitamin C; 78.65% ofwater.

The measured radical protection factor of the whole compound was 2.

EXAMPLE 8

Emulsion-based Fluid with Increased Vitamin A Content (Vitamin A²)

phase A: carbomer 0.05, glycerine 2.5, propylene glycol 0,5; dist. waterq.s. ad 100;

phase B: C₁₂-C₁₅-alkyl cetylic alcohol 1.5; stearate 0,1; olive oil 1,0;

phase C: triethanolamine 0,05;

phase D: complex with (a) through (d) containing 2% of quebrachoextract, 2% of silkworm extract, 0.1% of carbomer, 0.1% of TEA, water0.9%; as well as (h) retinyle palmitate and tocopherylacetate (1:1) asliposomes with phospholipids with 0.1% of Micrococcus luteus extract=0.1, retinyle palmitate (free) 0.5; phase E: perfume oil 0.2,preservant 0.3.

Phases A and B were warmed up to 65±2° C. while being stirred, and phaseB was homogenised in phase A. Then phase C was added at about 50° C. andhomogenised correspondingly. Subsequently, the mixture was cooled downto about 30° C. while being stirred, and phases D and E were added andmixed and homogenised thoroughly.

The radical protection factor of the complex amounted to 2100, and inthe fluid the RPF was around 20.

EXAMPLE 9

O/W Antismoke Day Cream

phase A: sorbitan monostearate 4; avocado oil 3; Oleyl oleate 8;

phase B: water q.s. ad 100; propylene glycol 2, glycerine 5 carbomer0.2;

phase B1: NaOH 0.4;

phase C: preservant 0.4;

phase D: active substance complex with (a) through (f) with vitaminsA,E,C,B 5;

phase E: perfume oil 0,5.

Phases A and B were made separately at 80° C. while stirring intensivelyand subsequently mixed, stirred and homogenised. After cooling down to60° C., phase B1 was added for neutralisation. After cooling down to 50°C., phase C was added. At 30° C. phases D and E were added to themixture one after another and homogenised; RPF=39.

EXAMPLE 10

Antismoke Night Cream

The cream provides a repair effect to a smoker's skin while at the sametime having a prophylactic effect for the day.

phase A: Vaseline 8.5; jojoba oil 3.0; stearic acid 3.8;

phase B: water q.s. ad 100; glycerine 5; carbomer 0.3;

phase C: triethanolamine 0,3;

phase D: preservant 0.4;

phase E: active substance complex (a) through (f) with vitamins A, E, C,B and 2% aloe vera 10.0; perfume oil 0.1.

The procedure was the same as in example 9; RPF =48.

EXAMPLE 11

Hand Cream Against Brown Smoker's Fingers

phase A: cetylic alcohol 8.5; stearic acid 3.8;

phase B: water q.s. ad 100; glycerine 2, carbomer 0.9;

phase C: triethanolamine 0,3;

phase D: vitamin E 1.0; aloe vera 1.0; preservant 0.4; active substancecomplex with (a) through (f) with vitamins A, E, C 5.0; perfume oil 1.4;whitening complex 1,0.

The procedure was the same as in example 9; RPF=35.

What is claimed is:
 1. Cosmetic active substance preparation with aradical protection factor, which comprises a content of (a) a productobtained by extraction of the bark of Quebracho blanco and subsequentenzymatic hydrolysis, containing at least 90 percent by weight ofproanthocyanidine oligomers and up to 10 percent by weight of gallicacid, where the content of (a), in the cosmetic active substanceprepartion ranges from 0.1 to 10 wt. % and wherein (a) is present as amicrocapsule with a concentration of the extraction product of 2 wt %;(b) an extract of silkworm obtained by extraction, containing thepeptide cecropine, amino acids and a vitamin mix, where the content of(b) ranges from 0.1 to 10 wt. %; (c) a non-ionic, cationic or anionichydrogel or mixture of hydrogels, where the content of (c) ranges from0.1 to 5 wt. %; (d) at least one phospholipid in the range of 0.1 up to30 wt. %; (e) water, wherein the radical protection factor is in therange 100 to 3500·10¹⁴ radicals per mg preparation; and wherein anassociation complex is between the phospholipids (d), at leastcomprising the components (a) and (b) and the gel (c) with the water(e).
 2. Preparation according to 1 further comprising (f) an ultrasoundproduct of a yeast containing at least 150 International units ofsuperoxide dismutase per ml, wherein the content of the decompositionproduct (f) is in the range from 0.1 to 4 wt. %, and (g) an extract ofacerola fruits Malpighia punidifolia, wherein the content (g) is in therange from 0.1 to 30 wt. %; related to the total weight of the activesubstance preparation each.
 3. Preparation according to 2 furthercomprising (h) a mixture of 0.1 wt. % if Micrococcus luteus extract,retinyl palmitate and tocopherylacetate in liposomal form prepared withphospholipids, and additionally tree retinyl palmitate and where theportion of the components contained in the preparation relative to thetotal weight of a cosmetic preparation are as follows: product of (a)and extract of (b) ranging from 0.1 to 10 wt. %, hydro gel according to(c) ranging from 0.1 to 5 wt. %, encapsulated retinyl palmitateaccording to (h) ranging from 0.001 to 5 wt. % encapsulatedtocopherylacetate according to (h) 0.001 to 5 wt. %, tree retinylpalmitate according to (h) 0.1 to 5 wt. %, phospholipids 0.2 to 5 wt. %.4. Preparation according to claim 3, wherein the portions of thecomponents lie within the following ranges: product of (a) and extractof (b) ranging from 0.5 to 3 wt. %, hydro gel according to (c) rangingfrom 0.1 to 3 wt. %, encapsulated retinyl palmitate according to (h)ranging from 0.05 to 2 wt. %, encapsulated tocopherylacetate accordingto (h) ranging from 0.05 to 1 wt. %, free retinyl palmitate according to(h) ranging from 0.5 to 2 wt. %.
 5. Preparation according to claim 1,wherein a radical protection factor in the range from 1000 to 3500·10¹⁴radicals per mg measured by determining the number of free radicals of asolution of a test substance (S₁) by electron spin resonance (ESR) ascompared with the ESR measurement result of the cosmetic activesubstance preparation according to the relationship RPF=(RC×RF)/PI,where RF=(S₁-S₂)/S₁; RC=concentration of the test substance (radicalsper ml); PI=concentration of the active substance preparation (mg perml).
 6. Preparation according to claim 1, wherein the product (a)contains at least 99 wt. % of proanthocyanidine oligomers and up to 1wt. % of gallic acid.
 7. Preparation according to claim 1, wherein theamino acids contained in (b) are selected from the group consisting ofaspertine acid, asparagine, threonine, serine, glutamic acid, proline,glycine, alanine, valine, cysteine, methionine, isoleucine, leucine,tyrosine, phenylalanine, lysine, histidine, and arginine.
 8. Preparationaccording to claim 1, wherein the vitamin mixture included in (b)comprises the vitamins B₁, B₂, B₅, B₆, B₈, B₉, B₁₂, PP, A, E and C. 9.Preparation according to claim 1, wherein the active substancepreparation contains an additional mixture of the vitamins A, E and C oreach of these vitamins individually.
 10. Preparation according to claim1, wherein the active substance preparation is a cosmetic compositionfurther comprising at least one of the following components: (1)extracts binding free radicals or moisture of (1.1) plants selected fromthe group consisting of acerola fruits (Malpighia punidifolia), CamelliaOleifera, Colunsonia canadensis and Hibiscus sabdariffa; or (1.2) algaeselected from the group consisting of omega plankton, providing a highportion of cerebrosid stimulants, microalgae of the chlorella speciesand macro algae of the ulva species with byssus (mussel silk) asbiotechnological protein fraction and subsequently associated withdextrine, wherein the product is in the mixture with peptide derivatesderived from a-MSH and associated with xanthin; (2) yeast decompositionproducts selected from the group consisting of baker's yeast, brewer'syeast, wine yeast and made according to an ultrasound treatment of theaqueous yeasts; (3) natural and synthetic polymers selected from thegroup consisting of chitosanglycolate, condensed products of desiccatedmilk, and activated fatty acids; (4) magnetically hard single crystalsof bariumhexaferrite having a coercitive field intensity of 3000-5000 Oeand a grain size of 50-1200 nm intercalated in or mixed with asymmetriclamellar aggregates of phospholipids and fluorocarbons; and (5) otheractive substances selected from the group consisting ofchitosanglycolate, hyaluronic acid, omega CH activator, behentrimoniumchloride, passion flower oil and carrier substances; (6) mixturesthereof.
 11. Preparation according to claim 1, wherein the concentrationof the product (a) and extract (b) in the active substance ranges from0.1 to 3 wt. % each.
 12. Preparation according to claim 1, wherein thepreparation comprises an additional portion if 0.1 to 20 wt. % of plantextracts selected from the group consisting of citrus peel or leafextracts (Citrus bigaradia, Citrus hystrix, Citrus aurantifolia,Citrofurtunella microcarpa, Citrus aurantium, Citrus reticulata),petitgrain extract (peel or fruit), extract of the Spanish cherry, kiwiextract (Actinidia chinensis), papaya fruit extract, (Caricae papayae),tea extract [leaves of green or black tea, leaves or bark of tea(Ceanthus velutinas)], prunus extract (Prunus armeniaca, Prunus dulcis,Prunus persica, Prunus domestica, Prunus spinosa, Prunus serotina,Prunus virginiana), extracts of the bark of the Mexican skin tree(Mimosa tenuiflora), angelica root extract (Angelica archangelica); andthe remaining portion of carrier substances.